US4072524A - Mixture yielding thermally stable photo-cross-linkable layers and foils - Google Patents

Mixture yielding thermally stable photo-cross-linkable layers and foils Download PDF

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Publication number
US4072524A
US4072524A US05/637,189 US63718975A US4072524A US 4072524 A US4072524 A US 4072524A US 63718975 A US63718975 A US 63718975A US 4072524 A US4072524 A US 4072524A
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composition
maleimide
weight
double bond
group
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Wolfgang Kleeberg
Roland Rubner
Wieland Bartel
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Siemens AG
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Siemens AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings

Definitions

  • This invention is concerned with mixtures yielding thermally stable, photo-crosslinkable layers and foils based on resins which contain allyl groups and are solid at room temperature, useful for the photographic preparation of layered structures.
  • compositions based on inert organic polymeric binding agents, thickening agents or matrices and acrylic or methacrylic compounds are known in the art from German Auslegeschriften Nos. 1,205,386, 1,200,130, and 1,915,571 and form German Offenlegungsschriften Nos. 1,906,668 and 2,149,056. These compositions are partly usable in foil form for the generation of patterns and structures.
  • the layered structures that can be produced from these compositions have only limited thermal stability.
  • relatively high concentrations of the photo-reactive acrylic or methacrylic compounds are necessary for producing high light sensitivity. This leads to sticky photosensitive layers which, when used in common photographic techniques with contact copies, must be exposed through protective films. Since the pattern and the photosensitive layer are not in direct contact with each other, inferior resolution results due to light diffraction.
  • thermally stable, photo-crosslinkable materials having a resin component containing allyl groups are known according to U.S. Pat. No. 3,462,267 and South-African Patent No. 05209.
  • the materials described therein however have the common disadvantage that layers having a thickness of no greater than about 1 to 5 ⁇ m have sufficient light sensitivity, but with increasing layer thicknesses the light sensitivity diminishes.
  • German Patent No. 2,130,904 that certain photo-cross linkable systems exhibit cross-linking speeds with layer thicknesses of more than 10 ⁇ m and these make possible the preparation of layered structures with sharp contours and good insulating properties.
  • These systems consist of a prepolymer component containing carboxylic acid allylester groups and compounds containing maleimide groups. A limiting effect for many applications of such systems is the limited thermal stability of the described prepolymer components.
  • the ring-positioned allyloxy groups of triallylcyanurate prepolymers in combination with compounds containing N-maleimide groups if exposed to actinic light, give high crosslinking speeds at layer thicknesses of more than 10 ⁇ m.
  • the light-sensitive mixtures according to this invention yield layers and films for the photographic preparation of thermally stable layered and film structures having sharp contours and of crosslinked coatings with good insulating properties.
  • the mixtures comprise triallylcyanurate prepolymers and/or triallylcyanurate precopolymers with compounds containing allyloxy and/or allylester groups and compounds containing at least one N-maleimide group whose maleimide C ⁇ C bond carries hydrogen, hydrogen and chlorine or hydrogen and methyl radicals, but preferably, hydrogen.
  • the photo-crosslinked coatings from these compositions obtained through the action of actinic light or the exposed photographic copies which can be produced with sharp contours by solvent etching are distinguished particularly by their high thermal stability, in addition to their insulating properites, i.e., high aging stability, high electric surface and bulk resistance, low water absorption and swelling.
  • Thermogravimetric analysis shows that the materials still have excellent stability at 300° C; with a heating rate of 5° C/min in air, a weight loss of 0.5%/min occurs at 300° C and the color of the material remains unchanged.
  • 2,130,904 using polydiallylorthophthalate as the resin component containing carboxylic acid allylester groups is higher by a factor of 6 at 300° C, and at the same time, the material is discolored black.
  • the materials according to the present invention are solder-bath proof and mechanically stable, and also exhibit at least a 140° C fatigue strength in air.
  • film-forming triallylcyanurate prepolymers and precopolymers of triallylcyanurate with compounds containing allyloxy- and/or allylester groups are suitable such as, phenylallylether, bisphenol-A-bisallylether, benzoic acid allylester, diallylphthalate, diallylisophthalate or diallylterephthalate, which can be prepared by methods known in the art from triallylcyanurate and other comonomers by polymerization up to a period shortly before gelation and by subsequent separation into soluble polymer or copolymer fractions and a monomer fraction, for instance, according to U.S. Pat. No. 3,030,341.
  • Suitable components of the mixtures according to the invention containing N-maleimide groups are aliphatically, aromatically or heterocyclically nitrogen-substituted maleimides, 3-chloromaleimides, 3-methylmaleimides such as, N-cyclohexylmaleimide, N-phenylmaleimide, N-phenylmaleimide substituted at the benzene nucleus (Preferred substituents have alkyl groups in the o-position) as well as compounds having two or more N-maleimide groupings, as are obtained from the corresponding polyfunctional amines, such as, for instance, hexamethylene diamine, m-phenylene diamine, p,p'-diaminodiphenyl or p,p'-diaminodiphenylmethane in a known manner by reaction of these compounds with maleic acid anyhdride.
  • N-arylmaleimides are used. N-aryl-maleimides, alkyl-substituted
  • the properties of the mixtures according to the invention can further be modified, in the kind and content of comonomer components of the triallylcyanurate prepolymers, by components of polymers compatible with polytriallylcyanurate.
  • polyester resins brings about increased flexibility.
  • Particularly suited are portions of unsaturated polyester resins, i.e., polymers containing maleate and/or fumarate structure elements.
  • unsaturated polyester resins i.e., polymers containing maleate and/or fumarate structure elements.
  • the conclusion may be drawn that the maleate or fumarate double bonds of the unsaturated polyester resins copolymerize upon exposure to light with the photoreactive allyloxy- and/or maleimide groups and thus participate in the cross-linking reaction and in the process also change the solubility of the polyester resins.
  • excellent edge sharpness and high resolution can be achieved also in the presence of the unsaturated polyester resins.
  • the content of unsaturated polyester resins may be up to 50% by weight; preferably, 5 to 30%.
  • the ratio of the allyl double bond equivalents, and as the case may be, including the maleate and/or fumarate double bond equivalents of unsaturated polyester components, to the N-maleimide double bond equivalents is equal to or greater than 1, and preferably 2 to 150.
  • polyester resins Preferably used are unsaturated polyester resins with an acid number smaller than 25 and preferably smaller than 10.
  • the polyester resins are prepared by known polyaddition or polycondensation methods (see, for instance, the book by J. Bjoerksten et al., Polyesters and their Application, Reinhold Publishing Corporation, New York, 1956). Many unsaturated polyester resins useful in the present invention are available as commercial products.
  • the cross-linking speed can be increased further by the addition of suitable photosensitizers and/or initiators, preferably in percentages of less than 2% by weight.
  • sensitizers and/or initiators are, for instance, Michler's ketone and/or benzoinether, 2-tert-butyl-9, 10-anthraquinone, 1, 2-benz-9, 10-anthraquinone, 4, 4'-bis-diethylamino)-benzophenone.
  • the mixtures according to the invention can be dissolved in inert organic solvents, applied to a substrate, e.g., a film, and cross-linked by exposure to actinic light after the solvent has evaporated.
  • a substrate e.g., a film
  • cross-linked by exposure to actinic light after the solvent has evaporated By pattern-wise exposure through a copying pattern and subsequent solvent treatment, copies with sharp contours are obtained.
  • the mixtures according to the invention can further be adjusted by components of up to 20% by weight of low-molecular to oligomeric, preferably liquid to viscous, olefinically-unsaturated compounds, preferably methacrylic, acrylic, vinyl, allyl, maleic acid or fumaric acid compounds, so that they can still be calendered and extruded at temperatures below 100° C down to room temperature and can therefore be processed in a technically advantageous manner into self-supporting polymer films or photopolymer films embedded between protective films.
  • low-molecular to oligomeric preferably liquid to viscous, olefinically-unsaturated compounds, preferably methacrylic, acrylic, vinyl, allyl, maleic acid or fumaric acid compounds
  • Suitable compounds are, for example, ethylene glycolbismethacrylate or -acrylate, diethyleneglycolbismethacrylate or -acrylate, trimethylolpropane trimethacrylate or -acrylate, glycerin trismethacrylate or -acrylate, 1,3-propanediolbismethacrylate or -acrylate, 1,2,4-butane trioltrimethacrylate or -acrylate, hydroquinone bismethacrylate or -acrylate, pentaerythritol tetramethacrylate or -acrylate, polyethyleneglycol bismethacrylate or -acrylate having molecular weights of 200 to 500, divinylsuccinate, divinylphthalate, allylbenzoate, diallylphthalate, maleic acid or fumaric acid diethylester. Methacrylic compounds are preferred.
  • contents of between 5 and 10% by weight are used.
  • the photopolymer films or foils obtainable in this manner are flexible, non sticky and can be exposed for generating patterns or structures through protective foils as well as, for direct contact with the pattern which is preferable. Subsequent solvent treatment then yields patterns and structures with particularly sharp contours. The additions do not adversely effect the light sensitivity of the photopolymers and the thermal stability of the photo-crosslinked layered structures.
  • the ready-to-use solutions of the photo-crosslinkable mixtures according to the invention and the ready-to-use films and foils prepared from the mixtures according to the invention have a high storage stability of more than 1/2 year at room temperature, if protected from light.
  • the mixtures according to the invention can be crosslinked by exposure to actinic light of any origin and kind as well known in the art.
  • the mixtures according to the invention contain components which are readily available and can be produced inexpensively and can be transformed by simple means into heat-resistant insulating layers, insulating layer structures and images.
  • the adhesion of the layers, layer structures and images produced on different substrates can be further improved by commonly used adhesive agents such as, the organo-silicon compounds, i.e., vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxy-propyltrimethoxysilane and particularly, by 2,4-diallyloxy-6-[3-(triethoxysilyl)propyl] aminotriazine. They can be provided in a known manner with seed layers for generating highly adhering electro-deposits.
  • the conditions for a wide and technically advantageous application of the photocrosslinked insulating materials therefore exist.
  • the mixtures according to the invention are generally suited for the applications described in the German Patent No. 2,130,904 and in addition, particularly for the preparation of thermally stable patterns and insulating, passivating and other protective layers and layered structures, especially as in aid in the manufacture or as part of components and circuits in electrotechnology, such as, solder protection layered structures on circuit boards for passivation structures on semiconductor components or easily removable photoresists for evaporation, sputtering, implantation and diffusion, ion-etching and other etching processes and for electroplating processes in the manufacture of semiconductor components.
  • PTAC Exactly 50 parts by weight PTAC, 3.75 parts by weight N-cyclohexylmaleimide and 0.5 parts by weight Michler's ketone were dissolved in 200 parts by volume trichloroethylene. The solution was filtered and centrifuged on glass substrates to form uniform films, which were 15 ⁇ m thick after the solvent had evaporated.
  • the films were exposed through a contact pattern for 20 sec to a 500-W (Very-high-pressure) mercury lamp placed at a distance of 23 cm from the films. Subsequently, well-adhering structures with sharp edges and high resolution (better than 20 ⁇ m) were produced by immersion in 1,1,1-trichloroethane for 2 minutes and a mixture of 1,1,1-trichloroethane and trichloroethylene (2:1) for 5 sec and washing with isopropanol. The film structures withstood the usual solder bath temperature of 260° C for 30 sec without damage.
  • PTAC Exactly 50 parts by weight PTAC, 3.75 parts by weight N-phenyl maleimide and 0.5 parts by weight Michler's ketone were dissolved in 200 parts by volume trichloroethylene and, as described in Example 1, centrifuged on aluminum foil to form films 15 ⁇ m thick, exposed for 20 sec and developed to form structures with sharp contours, great adhesitivity and resolution (better than 20 ⁇ m).
  • the electric bulk resistance of the crosslinked hardened films was higher than 10 14 ohm-cm as measured in accordance with DIN 53482 and the dielectric constant was about 3 at 10 3 Hz, as measured in accordance with DIN 53483.
  • PTAC Exactly 50 parts by weight PTAC, 3.75 parts by weight N-phenylmaleimide, 0.5 parts by weight Michler's ketone and 5 parts by weight 2,4-diallyloxy-6-[3(triethoxysilyl)propyl] aminotriazine were dissolved in 1000 parts by volume of trichloroethylene and processed by centrifuging on silicon wafers with an oxide surface to form films 1 ⁇ m thick.
  • a solution of 50 parts by weight PTAC, 3.75 parts by weight N-phenyl maleimide, and 0.5 parts by weight Michler's ketone in 200 parts by volume trichloroethylene films 15 ⁇ m thick were then applied to the thin films.
  • Similar structures with sharp edges were produced, which had particularly good adhesion.
  • Exactly 50 parts by weight PTAC, 3.75 parts by weight o-tolylmaleimide, 0.5 parts by weight Michler's ketone and 0.5 parts by weight benzoinisopropyl ether were dissolved in 200 parts by volume toluene and centrifuged on Al 2 O 3 ceramic substrates to form films 15 ⁇ m thick. As described in Example 1, the films were exposed for 10 sec through a contact-copy pattern and developed. The highly adhering layer structures with sharp contours withstood the usual solder bath temperature of 260° C for 1 min without damage. The electric bulk resistance of the crosslinked, hardened films was above 10 14 ohm-cm, measured in accordance with DIN 53482, and the dielectric constant, as measured in accordance with DIN 53483, was about 3 at 10 3 Hz.
  • PTAC Exactly 50 parts by weight PTAC, 3.75 parts by weight o-tolylmaleimide, 0.5 parts by weight Michler's ketone, 0.5 parts by weight benzoinisopropyl ether and 0.5 parts by weight 2,4-diallyloxy-6-[3(triethoxysylil)propyl] aminotriazine were dissolved in 200 parts by volume toluene and centrifuged on Al 2 O 3 ceramic substrates to form films 15 ⁇ m thick. By exposing and developing as in Example 4, corresponding layered structures with sharp contours were produced which exhibited particularly good adhesion.
  • PTAC Exactly 40 parts by weight PTAC, 10 parts by weight of a polyester resin with the acid number 20, containing the components fumaric acid, isophthalic acid and neopentylglycol in the mole ratio of 2:3:5, 3.75 parts by weight o-tolylmaleimide, 0.5 parts by weight Michler's ketone and 0.5 parts by weight benzoinisopropyl ether were dissolved in 200 parts by volume xylene, centrifuged on a 50- ⁇ m Cu foil to form films 15 ⁇ m thick and converted, as described in Example 1, into layered structures with sharp contours by exposing and developing. The elasticity and adhesion of the scratch-proof layers were demonstrated from the bending mandrel test according to DIN 53152.
  • Epoxy resin circuit boards with a final copper and tin surface were sprayed by means of a spray gun with the solution above and in this manner coated with films 30 ⁇ m thick. After exposing 30 sec through a contact copy in a Gyrex printer 900, developing and washing as in Example 1 and drying of the boards at 120° C for 30 min, perfectly soldered circuit boards with the solder resist layers intact were obtained in a wave soldering operation at 260° C. Similar results were obtained when the solution above contained additionally as a pigmentation component, 0.1 parts by weight Viktoria blue BOD Type 1246 (neutral) of the firm BASF.
  • PTAC Exactly 80 parts by weight of PTAC, 20 parts by weight of a polyester resin with the acid number 20, containing fumaric acid, isophthalic acid and neopentylglycol in the mole ratio 2:3:5, 7.5 parts by weight o-tolylmaleimide, 0.5 parts by weight Michler's ketone, 0.5 parts by weight benzoiniospropyl ether and 10 parts by weight diethyleneglycolbismethacrylate were mixed in a calender at room temperature and then calendered at 90° C to form sandwich foils with a polyethylene carrier and polyethylene terephthalate cover foils of 20 ⁇ m and a photoreactive intermediate layer of 60 ⁇ m.
  • the sandwich foils were led over a cylinder with a temperature of 90° C and laminated onto epoxy resin circuit boards with a final copper or tin surface.
  • the polyethyleneterephthalate cover foil was pulled off and the exposure was carried out with close contact between the negative copy and the photoreactive layer. In the latter case, structures with considerably sharper contours resulted.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US05/637,189 1974-12-06 1975-12-03 Mixture yielding thermally stable photo-cross-linkable layers and foils Expired - Lifetime US4072524A (en)

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DE19742457882 DE2457882B2 (de) 1974-12-06 1974-12-06 Waermebestaendige, lichtvernetzbare massen
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US (1) US4072524A (enrdf_load_stackoverflow)
JP (1) JPS51125483A (enrdf_load_stackoverflow)
AT (1) AT340771B (enrdf_load_stackoverflow)
BE (1) BE836269A (enrdf_load_stackoverflow)
CH (1) CH617950A5 (enrdf_load_stackoverflow)
DE (1) DE2457882B2 (enrdf_load_stackoverflow)
FR (1) FR2293467A1 (enrdf_load_stackoverflow)
GB (1) GB1525580A (enrdf_load_stackoverflow)
IT (1) IT1049880B (enrdf_load_stackoverflow)
NL (1) NL7514160A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615968A (en) * 1982-11-04 1986-10-07 Ciba-Geigy Corporation Compositions of matter which crosslink under the action of light in the presence of sensitizers
US5607814A (en) * 1992-08-07 1997-03-04 E. I. Du Pont De Nemours And Company Process and element for making a relief image using an IR sensitive layer
WO1997043696A1 (en) * 1996-05-16 1997-11-20 Napp Systems, Inc. Methods to increase the exposure sensitivity of photopolymerizable matrices and apparatus useful therefor
US6555593B1 (en) 1998-01-30 2003-04-29 Albemarle Corporation Photopolymerization compositions including maleimides and processes for using the same
US6605410B2 (en) 1993-06-25 2003-08-12 Polyfibron Technologies, Inc. Laser imaged printing plates

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS607261B2 (ja) * 1978-10-02 1985-02-23 旭化成株式会社 感光性エラストマ−組成物
JPH0739167B2 (ja) * 1984-10-29 1995-05-01 株式会社日立製作所 積層板の製造方法
DE102017200495A1 (de) * 2017-01-13 2018-04-26 Conti Temic Microelectronic Gmbh Verfahren zum Herstellen von einer Leiterplatte für ein Kraftfahrzeug

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060022A (en) * 1959-07-13 1962-10-23 Gen Aniline & Film Corp Image transfer process
US3147119A (en) * 1962-05-18 1964-09-01 Gen Aniline & Film Corp Photopolymerization of vinyl monomers with metal oxides as catalysts
US3462267A (en) * 1966-02-01 1969-08-19 Dynachem Corp Offset printing plates
US3469983A (en) * 1965-07-06 1969-09-30 Gaf Corp Preparation of photopolymer lithographic offset paper plates
US3619187A (en) * 1968-02-12 1971-11-09 Gaf Corp Process for preparing colored photoresists
US3832187A (en) * 1971-06-22 1974-08-27 Siemens Ag Single-phase film-forming photocross-linkable systems
US3905820A (en) * 1972-01-27 1975-09-16 Hoechst Ag Light sensitive copolymers, a process for their manufacture and copying compositions containing them
US3932401A (en) * 1974-01-31 1976-01-13 Minnesota Mining And Manufacturing Company Mixed acrylic acid/methacrylic acid esters of tris (hydroxyalkyl) isocyanurates
US3957512A (en) * 1973-02-22 1976-05-18 Siemens Aktiengesellschaft Method for the preparation of relief structures

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060022A (en) * 1959-07-13 1962-10-23 Gen Aniline & Film Corp Image transfer process
US3147119A (en) * 1962-05-18 1964-09-01 Gen Aniline & Film Corp Photopolymerization of vinyl monomers with metal oxides as catalysts
US3469983A (en) * 1965-07-06 1969-09-30 Gaf Corp Preparation of photopolymer lithographic offset paper plates
US3462267A (en) * 1966-02-01 1969-08-19 Dynachem Corp Offset printing plates
US3619187A (en) * 1968-02-12 1971-11-09 Gaf Corp Process for preparing colored photoresists
US3832187A (en) * 1971-06-22 1974-08-27 Siemens Ag Single-phase film-forming photocross-linkable systems
US3905820A (en) * 1972-01-27 1975-09-16 Hoechst Ag Light sensitive copolymers, a process for their manufacture and copying compositions containing them
US3957512A (en) * 1973-02-22 1976-05-18 Siemens Aktiengesellschaft Method for the preparation of relief structures
US3932401A (en) * 1974-01-31 1976-01-13 Minnesota Mining And Manufacturing Company Mixed acrylic acid/methacrylic acid esters of tris (hydroxyalkyl) isocyanurates

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615968A (en) * 1982-11-04 1986-10-07 Ciba-Geigy Corporation Compositions of matter which crosslink under the action of light in the presence of sensitizers
US5607814A (en) * 1992-08-07 1997-03-04 E. I. Du Pont De Nemours And Company Process and element for making a relief image using an IR sensitive layer
US6605410B2 (en) 1993-06-25 2003-08-12 Polyfibron Technologies, Inc. Laser imaged printing plates
WO1997043696A1 (en) * 1996-05-16 1997-11-20 Napp Systems, Inc. Methods to increase the exposure sensitivity of photopolymerizable matrices and apparatus useful therefor
US6555593B1 (en) 1998-01-30 2003-04-29 Albemarle Corporation Photopolymerization compositions including maleimides and processes for using the same

Also Published As

Publication number Publication date
CH617950A5 (enrdf_load_stackoverflow) 1980-06-30
ATA834875A (de) 1977-04-15
BE836269A (fr) 1976-04-01
FR2293467A1 (fr) 1976-07-02
DE2457882B2 (de) 1977-06-02
AT340771B (de) 1978-01-10
DE2457882A1 (de) 1976-06-16
JPS51125483A (en) 1976-11-01
NL7514160A (nl) 1976-06-09
FR2293467B1 (enrdf_load_stackoverflow) 1978-05-12
IT1049880B (it) 1981-02-10
GB1525580A (en) 1978-09-20

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